CN111013531A - Preparation method of titanium dioxide zeolite molecular sieve for adsorbing volatile organic pollutants - Google Patents
Preparation method of titanium dioxide zeolite molecular sieve for adsorbing volatile organic pollutants Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 116
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 62
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000010457 zeolite Substances 0.000 title claims abstract description 62
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 60
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002957 persistent organic pollutant Substances 0.000 title abstract description 5
- 238000001179 sorption measurement Methods 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- -1 methanol and ethanol Chemical class 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims description 44
- 229920005989 resin Polymers 0.000 claims description 44
- 238000002425 crystallisation Methods 0.000 claims description 35
- 230000008025 crystallization Effects 0.000 claims description 35
- 239000003463 adsorbent Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000012265 solid product Substances 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004088 foaming agent Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000002738 chelating agent Substances 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 96
- 150000002148 esters Chemical class 0.000 abstract description 4
- 150000002576 ketones Chemical class 0.000 abstract description 4
- 150000002605 large molecules Chemical class 0.000 abstract description 3
- 229920002521 macromolecule Polymers 0.000 abstract description 3
- 150000003384 small molecules Chemical class 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 231100000956 nontoxicity Toxicity 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 238000011049 filling Methods 0.000 description 28
- 239000012855 volatile organic compound Substances 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 239000010815 organic waste Substances 0.000 description 4
- 150000001555 benzenes Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 208000018706 hematopoietic system disease Diseases 0.000 description 1
- 238000007603 infrared drying Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 208000023504 respiratory system disease Diseases 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0532—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0536—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/12—Surface area
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/14—Pore volume
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Abstract
The invention provides a preparation method of a titanium dioxide zeolite molecular sieve for adsorbing volatile organic pollutants. The titanium dioxide produced by the process may be attached to the inner and/or outer surface of the zeolite molecular sieve. The titanium dioxide has a plurality of crystal phases, the crystal phase of the titanium dioxide prepared by the method is a rutile phase, and the adsorption capacity of the titanium dioxide of the crystal phase is relatively strong. The titanium dioxide zeolite molecular sieve obtained by the preparation method has the advantages of low synthesis cost, high crystallinity, large specific surface area, excellent molecular diffusion performance and stability, low price, no toxicity, no secondary pollution, high-efficiency adsorption capacity on large molecules such as esters, ketones and benzene series, small molecules such as methanol and ethanol, simple and economic preparation method, and suitability for large-scale industrial popularization and application.
Description
Technical Field
The invention relates to a preparation method of an adsorbent, in particular to a preparation method of a titanium dioxide zeolite molecular sieve, which is used for adsorbing volatile organic pollutants.
Background
In recent years, with the industrial development and the urbanization process accelerating, the problem of atmospheric environmental pollution is increasing, and a series of serious environmental and human health problems caused by Volatile Organic Compounds (VOCs) are receiving global attention. On one hand, VOCs discharged into the atmosphere can induce environmental pollution such as haze and the like; on the other hand, prolonged exposure to doses of VOCs may lead to respiratory or hematopoietic disorders.
There are many methods for treating VOCs, mainly including destruction techniques and recovery techniques, including absorption techniques, adsorption techniques, biological purification techniques, catalytic combustion techniques, and plasma purification techniques. At present, for the treatment of a plurality of low-concentration organic waste gases, the adsorption method is considered to be a process route with low operation cost, good purification effect, low energy consumption and ideal application, and has the widest application in the industrial aspect. The key of the adsorption method is the selection of an adsorption material and an adsorption process, and two adsorbents which are most widely applied in the industry at present are activated carbon and zeolite molecular sieves. Compared with active carbon, the zeolite molecular sieve has a regular pore channel structure and selective adsorption characteristics. In addition, it has high thermal stability, high specific surface area and pore volume. At present, zeolite molecular sieves are widely applied in the field of volatile organic compound treatment. Zeolite molecular sieves can be generally classified into natural zeolites and synthetic zeolites, but since natural zeolites are resource-restricted, synthetic zeolites are currently used in large quantities. However, the industrial application of the zeolite molecular sieve material still has the following problems: (1) the single pore size distribution causes the zeolite molecular sieve to only have adsorption effect on molecular VOCs with certain size, which is not beneficial to the adsorption of multi-component VOCs; (2) the agglomeration problem among zeolite particles can also reduce the adsorption efficiency and improve the pollutant treatment cost. (3) The existing material is only suitable for treating molecules with larger sizes, such as esters, ketones and benzene series, and has low adsorption efficiency on small molecular organic matters such as methanol and ethanol. (4) The current process for manufacturing the composite molecular sieve is complex and is easy to generate secondary pollution.
Therefore, there is an urgent need for a multifunctional, multi-functional, efficient, economical, nontoxic, inexpensive, and stable adsorbent to solve the above problems.
Disclosure of Invention
The invention aims to provide a volatile organic pollutant adsorbent which has high-efficiency adsorption capacity for small molecules such as methanol and ethanol and large molecules such as esters, ketones and benzene series and is simple in structure, cheap, non-toxic and easy to produce, and a preparation method thereof, and solves the problems of poor treatment effect, poor economy and poor compatibility of the small molecular organic matters in the prior art.
In order to achieve the purpose, the invention provides a preparation method of a titanium dioxide zeolite molecular sieve, which comprises the following steps:
an adsorbent comprising titanium dioxide and a zeolite molecular sieve, the titanium dioxide being attached to the zeolite molecular sieve. The titanium dioxide may be attached to the inner and/or outer surface of the zeolite molecular sieve. The zeolite molecular sieve is present in an amount of about 10 to about 90 weight percent and the titanium dioxide is present in an amount of about 10 to about 90 weight percent. Further, the weight ratio of the zeolite molecular sieve is preferably 60-80%, and the weight ratio of the titanium dioxide is preferably 20-40%. The above-mentioned ratio of titanium dioxide to zeolite molecular sieve is generally consistent with the ratio of low carbon number organic matter in the exhaust gas. In the invention, under the condition that the conventional organic matters are taken as main bodies, a small amount of low-carbon-number organic matters contained in the organic matters are treated, and the adsorbent can fully exert the respective characteristics of the zeolite molecular sieve and the titanium dioxide. If the proportion of the zeolite molecular sieve is too high, the proportion of titanium dioxide is correspondingly reduced, so that the treatment effect of the zeolite molecular sieve on low-carbon organic matters is reduced; and the proportion of the zeolite molecular sieve is too low, and the proportion of the titanium dioxide is correspondingly increased, so that the treatment effect of the zeolite molecular sieve on the conventional organic waste gas is reduced. On the other hand, if the surface area of the zeolite molecular sieve is completely occupied by titanium dioxide, the treatment effect of the conventional organic waste gas is also remarkably reduced by taking advantage of a part of the surface area of the zeolite molecular sieve to fully exert the function.
The invention also provides a preparation method of the adsorbent, which comprises the following steps:
(1) dissolving a titanium source, a silicon source, an aluminum source and ethanol in deionized water, adding a certain amount of propylene oxide as a chelating agent, fully stirring, and uniformly mixing to form gel;
(2) and adding a proper amount of macroporous resin into the gel to serve as a pore-foaming agent. After the macroporous resin fully adsorbs the gel, transferring the gel into a crystallization kettle with a polytetrafluoroethylene lining for crystallization treatment;
(3) and after crystallization is finished, washing, drying and roasting the crystallized product to obtain the titanium dioxide zeolite molecular sieve.
According to a particular embodiment of the invention, preferably, the method comprises the following particular steps:
(1) drying the macroporous resin at 30-90 deg.C for 2-5h, and oven drying;
(2) at room temperature, mixing and stirring a titanium source, a silicon source, an aluminum source, ethanol and deionized water uniformly;
(3) adding propylene oxide into the product obtained in the step (2), continuously stirring vigorously, and aging for 6-48h to obtain gel;
(4) adding a proper amount of dry macroporous resin as a pore-foaming agent into the gel, stirring for 2-4h, transferring the gel to a crystallization kettle with a polytetrafluoroethylene lining for crystallization treatment after the macroporous resin fully adsorbs the gel, wherein the crystallization temperature is 100-200 ℃, the crystallization time is 15-50h, and washing and drying the obtained solid product after crystallization is finished;
(5) and roasting the dried solid product in a muffle furnace at the temperature of 500-600 ℃, wherein the roasting time is 4-12h, and removing organic matters and macroporous resin in the product to obtain the titanium dioxide zeolite molecular sieve.
According to the specific embodiment of the present invention, preferably, the macroporous resin is one or a combination of two or more of a non-polar macroporous adsorption resin, a medium-polar macroporous adsorption resin and a polar macroporous adsorption resin; preferably a non-polar macroporous adsorbent resin.
Preferably, the macroporous resin is a low cost macroporous resin.
According to a specific embodiment of the present invention, preferably, the titanium source is one or a combination of two of titanium sulfate and titanium tetrachloride; more preferably inexpensive titanium tetrachloride.
According to the specific embodiment of the present invention, preferably, the silicon source is one or a combination of two or more of silica sol, silicic acid, white carbon black, sodium metasilicate and ethyl orthosilicate; more preferably tetraethoxysilane or silicic acid.
According to a specific embodiment of the present invention, preferably, the aluminum source is one or a combination of two or more of aluminum isopropoxide, pseudo-boehmite, aluminum nitrate, aluminum sulfate and boehmite; more preferably aluminum isopropoxide or sodium metaaluminate.
According to the specific embodiment of the present invention, preferably, the molar ratio of the silicon source, the aluminum source, the titanium source and the deionized water is 100SiO 2: mAl2O 3: n-titanium source: 3000H2O, wherein m = 0.17-5 and n = 10-40. The proportion of the gel to the macroporous resin is as follows: 5-40mL of gel, 5g of macroporous resin.
According to the specific embodiment of the present invention, preferably, the drying temperature of the macroporous resin is 40-70 ℃, and the drying time is 2-3 h; the aging time of the gel is 10-30 h; the crystallization temperature is 150-200 ℃, and the crystallization time is 16-40 h.
According to a specific embodiment of the present invention, preferably, a binder is added during the crystallization; the binder may be an organic binder and/or an inorganic binder. The binder may be silica sol and/or aluminum sol, etc.
According to a specific embodiment of the present invention, preferably, the drying temperature of the crystallized solid product is 80 to 160 ℃; more preferably from 90 to 120 ℃; the drying may be by microwave, infrared or hot air, etc.
According to the specific embodiment of the present invention, preferably, the calcination temperature is 550-600 ℃, and the calcination time is 8-10 h.
The invention also provides the titanium dioxide zeolite molecular sieve prepared by the method, wherein the silicon-aluminum ratio of the zeolite molecular sieve is 10-300, the micropore volume is 0.10-0.25cm3/g, the specific surface area is 600-1200m2/g, and the average particle size is 0.8-1.2 mm; preferably, the micropore volume of the zeolite is 0.15cm3/g, the mesopore volume is 0.26cm3/g, and the specific surface area is 1022m 2/g; the titanium dioxide may be attached to the inner and/or outer surface of the zeolite molecular sieve; titanium dioxide has a wide variety of crystalline phases, the most predominant of which are the anatase, brookite and rutile phases; preferably, the crystalline phase of the titanium dioxide is a relatively stable rutile phase.
According to a particular embodiment of the present invention, preferably, the titania zeolite molecular sieve has a particle size of between 100nm and 10 μm.
The organic matter generally refers to some organic binders and auxiliary agents introduced in the preparation process of the forming object, generally is a polymer, and the decomposition temperature of the organic binder and the auxiliary agents is about 300 ℃; therefore, when the temperature is too low, the treatment time is prolonged, and the removal is not easy to be thorough; and if the temperature is too high, the energy consumption is increased, and unnecessary loss is brought.
The adsorbent disclosed by the invention combines the advantages of titanium dioxide and zeolite molecular sieve by attaching titanium dioxide to the zeolite molecular sieve, and has the advantages of good technical compatibility, extremely large specific surface area, excellent molecular diffusion performance and the like. Not only has high-efficiency adsorption capacity for large molecules such as esters, ketones and benzene series, but also for small molecules such as methanol and ethanol, thereby greatly improving the treatment effect of organic waste gas. The composite adsorbent prepared by the method has the advantages of low cost, high efficiency, no toxicity, no secondary pollution and capability of making up the defects of the prior art. The preparation method of the adsorbent is simple and economic, and is suitable for large-scale industrial popularization and application.
Drawings
FIG. 1 is a schematic view of the microstructure of an adsorbent according to the present invention.
The notation in the figure is: 1-titanium dioxide and 2-zeolite molecular sieve.
Detailed Description
The technical solution of the present invention will be described in further detail below by way of comparative examples and examples, but is not limited to the contents of the examples.
Comparative example 1
Taking a zeolite molecular sieve (spherical with the diameter of 4 mm) without titanium dioxide as a filler, wherein the height of a filling layer is 15cm, the blowing concentration of methanol is 200mg/m3 at the wind speed of 2m/s, the temperature is 20 ℃, the humidity is 80% RH, the outlet methanol concentration of the filling layer is detected to be 150mg/m3 after 5 minutes, the outlet methanol concentration of the filling layer is detected to be 175mg/m3 after 6 minutes, the outlet methanol concentration of the filling layer is detected to be 193mg/m3 after 7 minutes, the outlet methanol concentration of the filling layer is detected to be 195mg/m3 after 8 minutes, the outlet methanol concentration of the filling layer is detected to be 196mg/m3 after 9 minutes, and the outlet methanol concentration of the filling layer is detected to be 196.3mg/m3 after 10 minutes.
Example 1
An adsorbent composite comprising a zeolite molecular sieve and titanium dioxide, the titanium dioxide being attached to the zeolite molecular sieve, either to the interior surface or to the exterior surface of the zeolite molecular sieve, the zeolite molecular sieve being present in an amount of about 80% by weight and the titanium dioxide being present in an amount of about 20% by weight.
The embodiment also provides a preparation method of the adsorbent, which comprises the following steps:
(1) drying the nonpolar macroporous adsorption resin in a 60 ℃ oven for 2h, and drying the water for later use;
(2) mixing 9.8g of titanium tetrachloride, 14g of deionized water and 10g of ethanol at room temperature, and uniformly stirring; adding 7.2g of silica sol and 0.1g of sodium metaaluminate, and continuing stirring until the silica sol and the sodium metaaluminate are dissolved;
(3) adding 0.1g of propylene oxide, continuously and violently stirring, and aging for 25h to obtain gel;
(4) adding 20g of dry nonpolar macroporous adsorption resin as a pore-forming agent into 41.2g of gel, stirring for 2h, after the macroporous adsorption resin fully adsorbs the gel, transferring the gel into a crystallization kettle with a polytetrafluoroethylene lining for crystallization treatment, wherein the crystallization temperature is 200 ℃, the crystallization time is 16h, and after the crystallization is finished, washing the obtained solid product and performing microwave drying at the temperature of 100 ℃;
(5) and (3) roasting the dried solid product in a muffle furnace at the temperature of 550 ℃ for 10h, and removing organic matters and macroporous resin to obtain the titanium dioxide zeolite molecular sieve with the particle size of between 100nm and 10 mu m.
The adsorbent is used as a filling layer, the height is 15cm, the blowing concentration is 200mg/m3 methanol at the wind speed of 2m/s, the temperature is 20 ℃, the humidity is 80% RH, the outlet methanol concentration of the filling layer is detected to be 35mg/m3 after 5 minutes, the outlet methanol concentration of the filling layer is detected to be 28mg/m3 after 6 minutes, the outlet methanol concentration of the filling layer is detected to be 23mg/m3 after 7 minutes, the outlet methanol concentration of the filling layer is detected to be 24mg/m3 after 8 minutes, the outlet methanol concentration of the filling layer is detected to be 24mg/m3 after 9 minutes, and the outlet methanol concentration of the filling layer is detected to be 26mg/m3 after 10 minutes.
Example 2
An adsorbent composite comprising a zeolite molecular sieve and titanium dioxide, the titanium dioxide being attached to the zeolite molecular sieve, either to the interior surface or to the exterior surface of the zeolite molecular sieve, the zeolite molecular sieve being present in an amount of about 70% by weight and the titanium dioxide being present in an amount of about 30% by weight.
(1) Drying the nonpolar macroporous adsorption resin in a 60 ℃ oven for 2h, and drying the water for later use;
(2) mixing 10.2g of titanium tetrachloride, 25.5g of deionized water and 10g of ethanol at room temperature, and uniformly stirring; adding 10g of ethyl orthosilicate and 0.1g of aluminum isopropoxide, and continuing stirring until the ethyl orthosilicate and the aluminum isopropoxide are dissolved;
(3) adding 0.1g of propylene oxide, continuously and violently stirring, and aging for 26 hours to obtain gel;
(4) adding 10g of dry nonpolar macroporous resin as a pore-forming agent into 55.9g of gel, stirring for 2h, after the macroporous resin fully adsorbs the gel, transferring the gel into a crystallization kettle with a polytetrafluoroethylene lining for crystallization treatment, wherein the crystallization temperature is 200 ℃, the crystallization time is 18h, and after the crystallization is finished, washing an obtained solid product and performing infrared drying at 105 ℃;
(5) and (3) roasting the dried solid product in a muffle furnace at the temperature of 550 ℃ for 10h, and removing organic matters and macroporous resin to obtain the titanium dioxide zeolite molecular sieve with the particle size of between 100nm and 10 mu m.
The adsorbent is used as a filling layer, the height is 15cm, the blowing concentration is 200mg/m3 methanol at the wind speed of 2m/s, the temperature is 20 ℃, the humidity is 80% RH, the outlet methanol concentration of the filling layer is detected to be 31mg/m3 after 5 minutes, the outlet methanol concentration of the filling layer is detected to be 24mg/m3 after 6 minutes, the outlet methanol concentration of the filling layer is detected to be 19mg/m3 after 7 minutes, the outlet methanol concentration of the filling layer is detected to be 20mg/m3 after 8 minutes, the outlet methanol concentration of the filling layer is detected to be 20mg/m3 after 9 minutes, and the outlet methanol concentration of the filling layer is detected to be 21mg/m3 after 10 minutes.
Example 3
An adsorbent composite comprising a zeolite molecular sieve and titanium dioxide, the titanium dioxide being attached to the zeolite molecular sieve, either to the interior surface or to the exterior surface of the zeolite molecular sieve, the zeolite molecular sieve being present in an amount of about 60% by weight and the titanium dioxide being present in an amount of about 40% by weight.
(1) Drying the nonpolar macroporous adsorption resin in a 60 ℃ oven for 2h, and drying the water for later use;
(2) at room temperature, 11g of titanium tetrachloride, 20.6g of deionized water and 10g of ethanol are mixed and stirred uniformly; adding 10g of ethyl orthosilicate and 0.05g of aluminum isopropoxide, and continuing stirring until the ethyl orthosilicate and the aluminum isopropoxide are dissolved;
(3) adding 0.1g of propylene oxide, continuously and violently stirring, and aging for 27 hours to obtain gel;
(4) adding 5g of dried nonpolar macroporous resin serving as a pore-forming agent into 41.75g of gel, stirring for 2h, after the macroporous resin fully adsorbs the gel, transferring the gel into a crystallization kettle with a polytetrafluoroethylene lining for crystallization treatment, wherein the crystallization temperature is 200 ℃, the crystallization time is 20h, and after the crystallization is finished, washing an obtained solid product and drying the solid product by hot air at 150 ℃;
(5) and (3) roasting the dried solid product in a muffle furnace at the temperature of 550 ℃ for 10h, and removing organic matters and macroporous resin to obtain the titanium dioxide zeolite molecular sieve with the particle size of between 100nm and 10 mu m.
The adsorbent is used as a filling layer, the height is 15cm, the blowing concentration is 200mg/m3 methanol at the wind speed of 2m/s, the temperature is 20 ℃, the humidity is 80% RH, the outlet methanol concentration of the filling layer is detected to be 42mg/m3 after 5 minutes, the outlet methanol concentration of the filling layer is detected to be 37mg/m3 after 6 minutes, the outlet methanol concentration of the filling layer is detected to be 33mg/m3 after 7 minutes, the outlet methanol concentration of the filling layer is detected to be 31mg/m3 after 8 minutes, the outlet methanol concentration of the filling layer is detected to be 26mg/m3 after 9 minutes, and the outlet methanol concentration of the filling layer is detected to be 25mg/m3 after 10 minutes.
Claims (13)
1. An adsorbent comprising titanium dioxide and a zeolite molecular sieve, the titanium dioxide being attached to the zeolite molecular sieve.
2. Composite material according to claim 1, characterized in that the weight ratio of the zeolitic molecular sieve is between 10 and 90% and the weight ratio of the titanium dioxide is between 10 and 90%.
3. Composite material according to claim 2, characterized in that the weight ratio of said zeolitic molecular sieve is comprised between 60 and 80% and the weight ratio of said titanium dioxide is comprised between 20 and 40%.
4. A method for producing the adsorbent according to claims 1 to 3, characterized by comprising the steps of: (1) dissolving a titanium source, a silicon source, an aluminum source and ethanol in deionized water, adding a certain amount of propylene oxide as a chelating agent, fully stirring, and uniformly mixing to form gel; (2) adding a proper amount of macroporous resin into the gel to serve as a pore-foaming agent; after the macroporous resin fully adsorbs the gel, transferring the gel into a crystallization kettle with a polytetrafluoroethylene lining for crystallization treatment; (3) and after crystallization is finished, washing, drying and roasting the crystallized product to obtain the titanium dioxide zeolite molecular sieve.
5. The preparation method according to claim 4, characterized by comprising the following specific steps: (1) drying the macroporous resin for 2-5h at the temperature of 30-90 ℃, and drying the water; (2) mixing and stirring a titanium source, a silicon source, an aluminum source, ethanol and deionized water uniformly at room temperature; (3) adding propylene oxide into the product obtained in the step (2), continuously stirring vigorously, and aging for 6-48h to obtain gel; (4) adding a proper amount of dry macroporous resin as a pore-foaming agent into the gel, stirring for 2-4h, transferring the gel to a crystallization kettle with a polytetrafluoroethylene lining for crystallization after the macroporous resin fully adsorbs the gel, wherein the crystallization temperature is 100 ℃ and 200 ℃, the crystallization time is 15-50h, and washing and drying the obtained solid product after crystallization is finished; (5) and roasting the dried solid product in a muffle furnace at the temperature of 500-600 ℃, wherein the roasting time is 4-12h, and removing organic matters and macroporous resin in the product to obtain the titanium dioxide zeolite molecular sieve.
6. The preparation method according to claim 4 or 5, wherein the macroporous resin is one or a combination of more than two of nonpolar macroporous adsorption resin, medium-polarity macroporous adsorption resin and polar macroporous adsorption resin; preferably non-polar macroporous adsorption resin; preferably, the macroporous resin is a low cost macroporous resin.
7. The production method according to claim 4, wherein the titanium source is one or a combination of two of titanium sulfate and titanium tetrachloride; preferably, inexpensive titanium tetrachloride.
8. The preparation method according to claim 4, wherein the silicon source is one or a combination of two or more of silica sol, silicic acid, white carbon black, sodium metasilicate and tetraethoxysilane; preferably tetraethoxysilane or silicic acid;
the preparation method according to claim 4, wherein the aluminum source is one or a combination of two or more of aluminum isopropoxide, pseudo-boehmite, aluminum nitrate, aluminum sulfate and boehmite; preferably aluminum isopropoxide or sodium metaaluminate.
9. The preparation method of claim 5, wherein the molar ratio of the silicon source to the aluminum source to the titanium source to the deionized water is 100SiO 2: mAl2O 3: n-titanium source: 3000H2O, wherein m is 0.17 to 5 and n is 10 to 40.
10. The proportion of the gel to the macroporous resin is as follows: 5-40mL of gel, 5g of macroporous resin.
11. The preparation method according to claim 5, wherein the drying temperature of the macroporous resin is 40-70 ℃, and the drying time is 2-3 h; the aging time of the gel is 10-30 h; the crystallization temperature is 150-; the roasting temperature is 550-600 ℃, and the time is 8-10 h.
12. The titania zeolite molecular sieve prepared by the process of any one of claims 1-11, wherein the molecular sieve has a silica to alumina ratio of 10-300, a micropore volume of 0.10-0.25cm3/g, a specific surface area of 600-1200m2/g, and an average particle size of 0.8-1.2 mm; preferably, the micropore volume of the zeolite is 0.15cm3/g, the mesopore volume is 0.26cm3/g, and the specific surface area is 1022m 2/g; the titanium dioxide may be attached to the inner and/or outer surface of the zeolite molecular sieve; titanium dioxide has a wide variety of crystalline phases, the most predominant of which are the anatase, brookite and rutile phases; preferably, the crystalline phase of the titanium dioxide is a relatively stable rutile phase.
13. The method of claim 4, wherein in step (1), the titania zeolite molecular sieve has a particle size of 100nm-10 μm.
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